Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
  • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
  • C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
  • Y10T428/296—Rubber, cellulosic or silicic material in coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31801—Of wax or waxy material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/3188—Next to cellulosic
  • Y10T428/31895—Paper or wood

Definitions

• This invention relates to the addition of perfluoroalkyl iodides to allyl glycidyl ether to produce perfluoro compounds which contain the reactive epoxide ring which is then capable of reacting with active-hydrogen-containing-compounds.
• the active hydrogen compounds include alcohols, carboxylic acids, phenols, mercaptans, mercaptoalcohols, thiourea, hydrogen sulfide and water.
• Another object is to produce derivatives of a perfluoro-epoxide compound which have improved solubility in water and organic solvents.
• Another object is to react active-hydrogen-containing-compounds with an extremely reactive epoxide group of a molecule also containing a perfluoro group.
• a further object is to react alcohols, carboxylic acids, phenols, mercaptans, mercaptoalcohols, thiourea, hydrogen sulfide, and water with perfluoroalkyl allyl glycidyl ether.
• a further object is to produce new compositions of matter and to advance the art.
• perfluoroalkyl iodides are completely fluorinated and contain no hydrogen or other substituents along the alkyl chain as evidenced by the alternative representation R f I. While individual iodides may be used, some advantages develop from the use of mixed alkyl groups, thereby making such a mixture suitable for use in this invention.
• Allyl glycidyl ether is readily available from commercial sources.
• the preparation of the perfluoroalkyl iodide-allyl glycidyl ether adduct may be carried out by a free radical reaction.
• perfluoroalkyl iodides examples include a mixture of C 6 -C 8 -C 10 iodides of approximately 1:2:1 ratio, perfluorodecyl iodide --C 10 F 21 I, and a mixture of C 10 -C 16 iodides.
• the presence of acidic contaminants in the perfluoroalkyl iodide may result in the polymerization of the allyl glycidyl ether.
• Bis-(4-t-butylcyclohexyl)peroxy dicarbonate is an alternate free-radical-generating catalyst which is useful. Five mole percent of the catalyst in acetone solution at 38°-39°C. for 22 hours gives complete utilization of the perfluoroalkyl iodide. The catalyst addition may be made by an initial and an interim charge. The perfluoroalkyl iodide-allyl glycidyl ether adducts are obtained in quantitative yields. Excellent epoxy values for the products are obtained.
• Ultraviolet irradiation is a highly efficient means of effecting the addition of the perfluoroalkyl iodides to allyl glycidyl ether. Irradiation may be supplied by a 140 watt Hanovia Alpine Lamp held at a distance of 2 cm. from the transparent quartz flask. A half-mole scale experiment with C 10 F 21 I and allyl glycidyl ether in acetone at 60°C. gave a 91.8% uptake of the perfluoroalkyl iodide in 3 hours and 94.6% in 6 hours. Conversion to colorless product is in the range of 95-97%.
• the product yield in the above procedure is usually in the vicinity of 90%.
• the product purity is subject to some variation. This may in part be due to epoxy ring opening as well as to the formulation of fluoroallenes.
• R f the perfluoroalkyl group
• G --CH 2 --CH--CH 2 --O-- in perfluoroalkyliodopropyl glycidyl ethers
• the product is the iodopropyl product.
• the product is dehydroiodinated due to the reaction of the basic catalyst.
• Acid catalysis has been found to be especially effective for the derivatives from hydroxyl compounds such as alcohols and phenols.
• Such catalysts include boron trifluoride etherate and stannic chloride.
• basic catalysts also produce a satisfactory product.
• Basic catalysis has been found to be especially effective for the derivatives from carboxylic acids.
• a suitable catalyst includes benzyldimethylamine. Acid catalysis also works to yield a satisfactory product.
• the active hydrogen containing compounds which are suitable to prepare the derivatives of this invention include alcohols, carboxylic acids, water, phenols, mercaptans, mercaptoalcohols, thiourea, and hydrogen sulfide.
• Alcohols which are suitable for use in this invention include any mono- or poly-functional alcohol such as but not limited to: methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, allyl alcohol, 2-methoxyethanol, 2-butoxyethanol, 2-(2-ethoxyethoxy) ethanol, 2-phenoxyethanol, ethylene glycol, glycerine, 1,3-butylene glycol, 1,4-butanediol, 1,2,4-butanetriol, butenediol, and butynediol.
• mono- or poly-functional alcohol such as but not limited to: methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, allyl alcohol
• Carboxylic acid which are suitable for use in this invention include any mono- or poly-functional acid such as but not limited to any of the following: acetic, propionic, butyric, formic, octanoic, lauric, stearic, oleic, succinic, glutaric, adipic, benzoic, and phthalic acids.
• Suitable phenols which may be used include, but are not limited to the following: phenol, o-cresol, p-cresol, m-cresol, o-chlorophenol, p-chlorophenol, m-chlorophenol, resorcinol, hydroquinone, and hydroquinonemonomethyl ether.
• Suitable mercaptans include both aliphatic and aromatic, mono- and poly-mercaptans such as, but not limited to, any of the following: butyl mercaptan, heptane mercaptan, 1-decanethiol, lauryl mercaptan, thiophenol, thiocresol, o-toluenethiol, and m-toluenethiol.
• Suitable mercaptoalcohols include such as, but not limited to, the following: mercaptoethanol, mercaptopropanol, and mercaptobutanol.
• the present reaction may be carried out in either a batch or continuous manner. While, for small scale preparations, the bath reaction is more convenient, the continuous reaction is more useful for commercial operations.
• the reaction is carried out at either atmospheric or super atmospheric pressure depending on the reactants.
• the reaction temperature varies and depends primarily upon convenience. Accordingly, the temperature is generally about 70°-120°C., preferably 80°-100°C.
• the reaction may be carried out in either a solvent or a non-solvent system.
• the time of reaction may vary from 1 to 30 hours or more depending upon the other conditions.
• reaction sequence leading to adducts of perfluoroalkyl-allyl glycidyl ethers and alcohols may be represented by the equation as follows: ##EQU5##
• the resulting adducts may be termed 3-perfluoroalkyl-allyloxy-2-alkoxyl-1-propanols.
• This reaction of the alcohol with the epoxide link of the perfluoro compound in the following cases was performed by catalysis by 0.8 mole percent boron trifluoride etherate per 1 mole of perfluoroalkyl-allyl glycidyl ether adduct at 90°C. over a 2-3 hour period. A 5 to 10% excess of the alcohol i.e., 1.05-1.10 mole/mole over the amount calculated on the epoxy equivalence of the glycidyl ether was used.
• the perfluoroalkyl group in each of these reactions was in the nature of a C 6 , C 8 , C 10 mixture of approximately a 1:2:1 ratio.
• the reaction alcohols are listed below.
• reaction sequence leading to adducts of perfluoroalkyl-allyl glycidyl ethers and carboxylic acids may be represented by the equation as follows: ##EQU7##
• the resulting adducts may be termed 3-perfluoroalkyl-allyloxy-2-hydroxypropyl carboxylates.
• the resulting adducts are 3-perfluoroalkyl-allyloxy-2-hydroxy-propylphenylethers.
• a mixture of 53g (.10 mole) perfluorooctylallyl glycidyl ether, 10g (.11 mole) butyl mercaptan and .5 ml. benzyldimethylamine is heated at 85°-90°C. with stirring, in a nitrogen atmosphere for a 3 hr. period. Gas chromatographic examination would reveal the complete utilization of the glycidyl ether. The resulting mixture is then subjected to heating at 95°C. and 10 mm. to remove excess butyl mercaptan.
• the reaction product consists of 1-thiobutyl-3-perfluorooctylallyloxy-2-propanol in an amount of 62 grams.
• Example XXX The procedure of Example XXX is repeated except that 22 g. of lauryl mercaptan is employed as the mercaptan component.
• the reaction product consists of 1-thiolauryl-3-perfluorooctylallyloxy-2-propanol in an amount of 72 gm.
• Example XXX The procedure of Example XXX is repeated except that 9g. of mercaptoethanol is employed as the mercaptan component.
• the reaction product consists of 1-( ⁇ -hydroxyethylmercapto)-3-perfluorooctylallyloxy-2-propanol in the amount of 60 gm.
• a stirred mixture of 106 g. (.20 mole) perfluorooctylallyl glycidyl ether and 1.0 ml. benzyldimethylamine is heated at 85°C. with concurrent introduction of an equimolar amount of gaseous hydrogen sulfide.
• Gas liquid chromatography indicates full utilization of the glycidyl ether.
• the reaction product comprises the addition product of hydrogen sulfide and perfluorooctylallyl glycidyl ether.

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Cited By (11)

Citations (2)

• 1972
  • 1972-07-07 US US05/269,911 patent/US3952066A/en not_active Expired - Lifetime
• 1973
  • 1973-05-01 CA CA170,190A patent/CA1013372A/en not_active Expired
  • 1973-06-27 CH CH938273A patent/CH585740A5/xx not_active IP Right Cessation
  • 1973-07-07 JP JP7702873A patent/JPS5530495B2/ja not_active Expired

Patent Citations (2)

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